Active polymeric filters

ABSTRACT

A compound includes a polymer where the polymer includes a pendant dioxirane moiety. Cost-effective, facilitated generation of a polymer including a pendant dioxirane moiety allows for the compound to be disposable or be easily recycled. The compound can be used in air purification and liquid purification to not only remove particulate matter, but also to destroy microorganisms and remove volatile organic compounds.

This application claims the benefit of International Application SerialNo. PCT/US2011/056683, filed on Oct. 18, 2011, the entire disclosure ofwhich is hereby incorporated by reference for all purposes in itsentirety as if fully set forth herein.

FIELD

The present technology relates to compounds for active chemical filtersfor gas and liquid purification.

BACKGROUND

The following description is provided to assist the understanding of thereader. None of the information provided or references cited is admittedto be prior art to the present technology.

Demand is increasing worldwide for reliable, efficient, and low-cost airtreatment systems in confined spaces. Air contaminants include volatileorganic compounds (VOCs), inorganic/organic particulates, and biologicalparticulates such as bacteria, fungi (mold), and various otherbiological contaminants (including viruses). Many filtration strategiesexist for purifying air, yet they suffer from various drawbacks.

Physical filtration strategies remove most particulates, but have littleeffect on VOCs. They can also serve as a breeding ground formicroorganisms, which compromise the flow rate of air through thefilter.

Electrostatic filtration strategies improve on basic physical filtrationwithout further restricting airflow. However, energy is required tocharge the filter. Importantly, electrostatic filtration strategies donot address VOCs and they do not kill bacteria. They can therefore serveas a breeding ground for microorganisms.

Photochemical filters generally include TiO₂ as an agent to generatesinglet oxygen, which can kill microorganisms. While generallyeffective, and despite the TiO₂ having a long lifetime, the lifetime ofthe active species of the filter, e.g. the singlet oxygen, is veryshort. In addition, favorable TiO₂ kinetics are limited to a smallnumber of surfaces.

Active Chemical filtration is effective, but the lifetime may be tooshort. In addition, the filter may be expensive and/or burdensome toreplace or recharge. Other problems are that the active chemical can bea health hazard (e.g. ozone), and/or very slow kinetics (e.g.peroxymonosulfate).

SUMMARY

The present technology provides for a polymer having a pendant dioxiranemoiety that is reactive toward microorganisms and VOCs, and is capableof oxidizing those materials to either kill them or render themharmless. This is achieved by configuring the polymer into a filterthrough which a contaminated fluid, i.e. gas or liquid, may be passed.As the fluid passes through the filter, at least a portion of thecontaminant may be oxidized by the pendant dioxirane moiety, thuspurifying the fluid and reducing or eliminating the amount ofcontaminant present in the fluid.

In one aspect, a polymer includes a pendant dioxirane moiety. In variousembodiments, the pendant dioxirane moiety is generally represented byFormula I or Formula II:

In Formula I, the pendant dioxirane may be part of a side chainextending off the backbone of the polymer. In Formula II, the pendantdioxirane may be part of the backbone of the polymer. In the aboveFormula I, R¹ may be a bond (i.e. absent), alkylene, perhaloalkylene,cycloalkylene, arylene, heteroarylene, heterocyclylene, amino, carbonyl,carboxyl, alkylcarboxy, carboxyalkyl or alkylcarboxyalkyl; R² may be anelectron withdrawing group; and R³ may be a hydrogen, alkyl,perhaloalkyl, cycloalkyl, aryl, heteroaryl, heterocyclyl, amino,carbonyl, carboxyl, alkylcarboxy, carboxyalkyl or alkylcarboxyalkyl.

In another aspect, a process is provided including providing a firstpolymer including an oxo group and reacting the oxo group withperoxymonosulfate to form a second polymer including a pendant dioxiranemoiety.

In another aspect, an article is provided including a polymer whichincludes a pendant dioxirane moiety. In various embodiments, thisarticle is a gas or liquid filter.

In a further aspect, a method of gas purification is provided includingpassing gas through a filter including a polymer including a pendantdioxirane moiety and the gas includes a biological contaminant orchemical contaminant. In some embodiments, the gas is air.

In another aspect, a method of fluid purification is provided includingpassing a fluid, such a liquid or gas, through a filter, where thefilter includes a polymer including a pendant dioxirane moiety and thefluid includes a biological contaminant or chemical contaminant.

In another aspect, a method is provided including providing a filterincluding a polymer, the polymer including ketone moieties, andconverting the ketone moieties to dioxirane moieties by reacting thepolymer with peroxymonosulfate.

The foregoing summary is illustrative only and is not intended to be inany way limiting. In addition to the illustrative aspects, embodimentsand features described above, further aspects, embodiments and featureswill become apparent by reference to the following drawings and thedetailed description.

DETAILED DESCRIPTION

The illustrative embodiments described in the detailed description andclaims are not meant to be limiting. Other embodiments may be utilized,and other changes may be made, without departing from the spirit orscope of the subject matter presented here.

The present technology is described herein using several definitions, asset forth throughout the specification.

As used herein, unless otherwise stated, the singular forms “a,” “an,”and “the” include plural reference. Thus, for example, a reference to “acell” includes a plurality of cells, and a reference to “a molecule” isa reference to one or more molecules.

As used herein, “about” will be understood by persons of ordinary skillin the art and will vary to some extent depending upon the context inwhich it is used. If there are uses of the term which are not clear topersons of ordinary skill in the art, given the context in which it isused, “about” will mean up to plus or minus 10% of the particular term.

Alkyl groups include straight chain, branched chain, or cyclic alkylgroups having 1 to 24 carbons or the number of carbons indicated herein.In some embodiments, an alkyl group has from 1 to 16 carbon atoms, from1 to 12 carbons, from 1 to 8 carbons or, in some embodiments, from 1 to6, or 1, 2, 3, 4 or 5 carbon atoms. Examples of straight chain alkylgroups include groups such as methyl, ethyl, n-propyl, n-butyl,n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branchedalkyl groups include, but are not limited to, isopropyl, iso-butyl,sec-butyl, tert-butyl, neopentyl, isopentyl, and 2,2-dimethylpropylgroups. In some embodiments, the alkyl groups may be substituted alkylgroups.

Cycloalkyl groups are cyclic alkyl groups having from 3 to 10 carbonatoms. In some embodiments, the cycloalkyl group has 3 to 7 ringmembers, whereas in other embodiments the number of ring carbon atomsrange from 3 to 5, 3 to 6, or 5, 6 or 7. Cycloalkyl groups furtherinclude monocyclic, bicyclic and polycyclic ring systems. Monocyclicgroups include, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,and cycloheptyl groups. Bicyclic and polycyclic cycloalkyl groupsinclude bridged or fused rings, such as, but not limited to,bicyclo[3.2.1]octane, decalinyl, and the like. Cycloalkyl groups includerings that are substituted with straight or branched chain alkyl groupsas defined above. In some embodiments, the cycloalkyl groups aresubstituted cycloalkyl groups. Representative substituted alkenyl groupsmay be mono-substituted or substituted more than once, such as, but notlimited to, mono-, di- or tri-substituted with substituents such asthose listed above. Representative substituted alkyl groups may bemono-substituted or substituted more than once, such as, but not limitedto, mono-, di- or tri-substituted with substituents such as those listedabove.

Alkenyl groups include straight and branched chain alkyl groups asdefined above, except that at least one double bond exists between twocarbon atoms. Thus, alkenyl groups have from 2 to 24 carbon atoms, andtypically from 2 to 10 carbons or, in some embodiments, from 2 to 8, 2to 6, or 2 to 4 carbon atoms. Examples include, but are not limited tovinyl, allyl, —CH═CH(CH₃), —CH═C(CH₃)₂, —C(CH₃)═CH₂, —C(CH₃)═CH(CH₃),—C(CH₂CH₃)═CH₂, among others. Representative substituted alkenyl groupsmay be mono-substituted or substituted more than once, such as, but notlimited to, mono-, di- or tri-substituted with substituents such asthose listed above.

The terms “alkylene,” “cycloalkylene,” and “alkenylene,” alone or aspart of another substituent means a divalent radical derived from analkyl, cycloalkyl, or alkenyl group, respectively, as exemplified by—CH₂CH₂CH₂CH₂—. For alkylene, cycloalkylene, and alkenylene linkinggroups, no orientation of the linking group is implied.

The term “amine” (or “amino”) as used herein refers to —NHR and —NRR′groups, where R, and R′ are independently hydrogen, or a substituted orunsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or aralkyl groupas defined herein. Examples of amino groups include —NH₂, methylamino,dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino,phenylamino, benzylamino, and the like.

The term “oxo” refers to a divalent oxygen group. While the termincludes doubly bonded oxygen, such as that found in a carbonyl group,as used herein, the term oxo explicitly includes singly bonded oxygen ofthe form —O— which is part of a polymer backbone. Thus, an oxo group maybe part of an ether linkage (—O—), an ester linkage (—O—C(O)—), acarbonate linkage (—O—C(O)O—), a carbamate linkage (—O—C(O)NH— or —O—C(O)NR—), and the like.

“Substituted” refers to a chemical group as described herein thatfurther includes one or more substituents, such as lower alkyl(including substituted lower alkyl such as haloalkyl, hydroxyalkyl,aminoalkyl), aryl (including substituted aryl), acyl, halogen, hydroxy,amino, alkoxy, alkylamino, acylamino, thioamido, acyloxy, aryloxy,aryloxyalkyl, carboxy, thiol, sulfide, sulfonyl, oxo, both saturated andunsaturated cyclic hydrocarbons (e.g., cycloalkyl, cycloalkenyl),cycloheteroalkyls and the like. These groups may be attached to anycarbon or substituent of the alkyl, alkenyl, alkynyl, aryl,cycloheteroalkyl, alkylene, alkenylene, alkynylene, arylene, heteromoieties. Additionally, the substituents may be pendent from, orintegral to, the carbon chain itself

The present technology provides for a polymer having a pendant dioxiranemoiety that is reactive toward microorganisms and VOCs, and is capableof oxidizing those materials to either kill them or render themharmless. In some embodiments, this is achieved by configuring thepolymer into a filter through which a contaminated fluid, i.e. gas orliquid, may be passed. The contaminated fluid may include a contaminantsuch as a microorganism or VOC. As the fluid passes through the filter,at least a portion of the contaminant may be oxidized by the pendantdioxirane moiety, thus purifying the fluid and reducing or eliminatingthe amount of contaminant present in the fluid.

In one aspect, a polymer is provided including a pendant dioxiranemoiety. Dioxiranes are cyclic peroxides which may be prepared by theoxidation of carbonyl groups, using various peroxy carbonyl species. Thependant dioxirane may include a member of the cyclic group that iswithin the polymer backbone (i.e. by oxidation of a carbonyl group,where the carbon atom is located in the polymer chain), or the pendantdioxirane may be part of an organic group, or side chain of the polymerbackbone.

In one embodiment, the polymer includes a unit represented by Formula Ior II:

In Formula I, the pendant dioxirane is part of a side chain extendingoff the backbone of the polymer. In Formula II, the pendant dioxirane ispart of the backbone of the polymer. In Formulas I, R¹ is a bond (i.e.R¹ is absent), or R¹ is alkylene, perhaloalkylene, cycloalkylene,arylene, heteroarylene, heterocyclylene, amino, carbonyl, carboxyl,alkylcarboxy, carboxyalkyl or alkylcarboxyalkyl; R² includes an electronwithdrawing group; and R³ is H, alkyl, perhaloalkyl, cycloalkyl, aryl,heteroaryl, heterocyclyl, amino, carbonyl, carboxyl, alkylcarboxy,carboxyalkyl or alkylcarboxyalkyl.

In Formula I, the electron withdrawing group is a —N⁺R⁴R⁵R⁶ group, ahalogen, NO₂, C(O)H, a CO₂R⁷ group, an alkoxy group, or a perhaloalkylgroup, where R⁴, R⁵, R⁶, and R⁷ are each independently H, alkyl, orcycloalkyl. According to some embodiments, the electron withdrawinggroup is a perfluoroalkyl.

In various embodiments, R¹ is an alkylene, perhaloalkylene, carbonyl,carboxyl, alkylcarboxyl, carboxyalkyl, or alkylcarboxyalkyl.

The polymer backbone may generally be any polymer which includes acarbonyl group, to which a moiety containing a carbonyl group may beattached. For example, the polymer backbone may be a polyolefin, apolyalkylene terephthalate, a polyacrylate, a polylactate, apolycarbonate, a polyester, a polysaccharide, a polyacetate, apolystyrene maleic anhydride, a polyurethane, a polyamide, apolyacrylamide, a polymethacrylate, a poly(methyl)methacrylate, anaramid, or a co-polymer of any two or more such polymers.

In other embodiments, the polymer includes a unit represented by FormulaIII or IV:

In Formulas III and IV, R¹ is absent (i.e. a bond between the polymerbackbone and the methylene group of the dioxirane), or R¹ is alkylene,perhaloalkylene, cycloalkylene, arylene, heteroarylene, heterocyclylene,amino, carbonyl, carboxyl, alkylcarboxy, carboxyalkyl oralkylcarboxyalkyl; R² is an electron withdrawing group; R⁸ is —N⁺R⁴R⁵ oralkyl; R⁹ is —N⁺R⁴R⁵ or alkyl; each R⁴ is independently H, alkyl, orcycloalkyl; each R⁵ is independently H, alkyl, or cycloalkyl; R⁶ is H,alkyl, or cycloalkyl; and R⁷ is H, alkyl, or cycloalkyl. Suitableelection withdrawing groups include, but are not limited to, —N⁺R⁴R⁵R⁶groups, a halogen, NO₂, C(O)H, a CO₂R⁷ group, an alkoxy group, or aperhaloalkyl group, where R⁴, R⁵, R⁶, and R⁷ are each independently H,alkyl, or cycloalkyl. According to some embodiments, the electronwithdrawing group of Formula III is a perfluoroalkyl. According to someembodiments, R¹ is an alkylene, perhaloalkylene, carbonyl, carboxyl,alkylcarboxyl, carboxyalkyl, or alkylcarboxyalkyl. In some embodimentsof Formula III, R¹ is absent, or R¹ is a C₁-C₆ alkylene or —N⁺R⁴R⁵; andR² is alkylene, perhaloalkylene, CO₂R⁷ or —N⁺R⁴R⁵R⁶. In someembodiments, of Formula IV, R⁸ is —N⁺R⁴R⁵ or alkyl; and R⁹ is —N⁺R⁴R⁵ oralkyl. In some embodiments, the polymer includes a repeat unitrepresented by Formula III where R¹ is absent, methylene or ethylene;and R² is H, methyl, ethyl, or trimethylammonium. In some embodiments,the polymer includes a repeat unit represented by Formula IV where R⁸ isC₁-C₈ alkylene; R⁹ is —N⁺R⁴R⁵, R⁴ is alkyl; and R⁵ is alkyl. In someembodiments, R⁸ is —N⁺R⁴R⁵; R⁹ is —N⁺R⁴R⁵; R⁴ is alkyl; and R⁵ is alkyl.

The dioxirane moiety of the polymer is a highly reactive group, yet ithas a sufficiently long lifetime to make practical use of the dioxirane.As noted, above, the polymers with the pendant dioxiranes may begenerated from polymers having at least one carbonyl (CO) group. Thisbroad spectrum of options allows the properties of the polymer to bemodified for a wide range of applications.

For example, to increase compatibility with different solutions, thepolymer may be selected to be either more hydrophilic or morehydrophobic. If the polymer is to be used to purify aqueous solutions,it may be desirable to have a more hydrophilic polymer, containinggroups such as carboxyl groups, hydroxyl groups, ethers, amines, orammonium groups. If the polymer is to be used to purify a contaminatedoil, the polymer may include more alkyl or aryl groups to increase thehydrophobicity of the polymer. Furthermore, the ability to use differentpolymers together allows for a very broad scope of intended applicationenvironments, and for a wide range of contaminants to be oxidized.

In another aspect, a process is provided preparing a polymer having apendant dioxirane moiety. For example, the process may include providinga first polymer including an carbonyl group and contacting the carbonylgroup with a peroxymonosulfate to form a second polymer that includesthe pendant dioxirane moiety. The process may include combining thefirst polymer with a solution that includes the peroxymonosulfate. Invarious embodiments, the pendant dioxirane moiety, i.e. the secondpolymer, is represented by any of Formulas I, II, III, or IV asdescribed above.

In various embodiments, the first polymer includes a polyalkyleneterephthalate, a polyacrylate, a polylactate, a polycarbonate, apolyester, a polysaccharide, a polyacetate, a polystyrene maleicanhydride, a polyurethane, a polyamide, a polyurea, a polyacrylamide, apolymethacrylate, a poly(methyl)methacrylate, an aramid, or a co-polymerof any two or more such polymers. In some embodiments, the first polymerincludes a poly(alkyl-2-ketoalkenoate). In certain embodiments, thepoly(alkyl-2-ketoalkenoate) is poly(methyl-2-keto-3-butenoate) orpoly(methyl-2-keto-4-pentenoate).

Suitable peroxymonosulfates include, but are not limited to, those suchas alkali metal peoroxymonosulfates, ammonium peroxymonosulfates, andphosphonium peroxymonosulfates. Illustrative peroxymonosulfates include,but are not limited to, lithium peroxymonosulfate, sodiumperoxymonosulfate, potassium peroxymonosulfate, tetramethylammoniumperoxymonosulfate, tetraethylammonium peroxymonosulfate,trimethylammonium peroxymonosulfate, triethylammonium peroxymonosulfate,triisopropylammonium peroxymonosulfate, tetraisopropylammoniumperoxymonosulfate, and benzyltriphenylphosphonium peroxymonosulfate.

Peroxymonosulfate oxidants are available commercially, for example,potassium peroxymonosulfate sold under the name OXONE® (DuPont,Wilmington Del.). Other forms of peroxymonosulfate are available withdifferent counterions, such as alkali metal cations, alkali earth metalcations, ammonium cations, tetraalkylammonium cations, and the like. Forexample, a form of peroxymonosulfate having a tetrabutylammonium cationis commercially available under the name OXONE® tetrabutylammonium salt(Sigma-Aldrich, St. Louis, Mo.).

The peroxymonosulfate solution may be prepared from water and aperoxymonosulfate compound at a concentration from about 0.1 millimolarto about 1 molar, or in some examples from about 1 millimolar to about100 millimolar. In some examples, a peroxymonosulfate solution mayinclude a base or buffer to adjust the pH. The solution may have a pHbetween about 4 and about 10, or in some examples, the pH may be about7. Suitable bases for adjusting the pH of the peroxymonosulfate solutioninclude carbonates and bicarbonates of alkali metals and alkali earthmetals, e.g., sodium bicarbonate, potassium carbonate, and the like. Insome examples, a peroxymonosulfate solution may include other componentswhich may function as processing aides, wetting aids, or the like. Forexample, the peroxymonosulfate solution may include organic solvents,surfactants, and/or phase transfer reagents. Suitable organic solventsinclude water miscible organic solvents, for example acetonitrile,alcohols, or the like. Suitable surfactants include anionic, cationic,and nonionic surfactants. Suitable phase transfer reagents include, forexample, organic quaternary ammonium salts, e.g., tetrabutylammoniumbromide. In some examples, the surfactant may also function as a phasetransfer reagent, for example, the quaternary ammonium surfactant cetyltrimethylammonium bromide. In some examples, the peroxymonosulfate maybe provided as a quaternary ammonium salt, for example, the OXONE®tetrabutylammonium salt.

In one illustrative example, the process includes contacting a firstpolymer having a carbonyl group with a mixture of water and KHSO₅(potassium peroxymonosulfate). After completion, the polymer with apendant dioxirane is recovered and isolated.

In another aspect, an article is provided including a polymer whichincludes a pendant dioxirane moiety. Such polymers may be as describedabove with regard to Formulas I, II, III and IV. In some embodiments,the article is a fibrous woven substrate such as a filter. Such filtersmay be prepared by forming the polymer into fibers which are thenfabricated into filters, or the polymers may be blown into a foam whichthen fabricated into a filter. The polymers may be formed into thefilter either before or after the pendant dioxirane moiety has beenformed on the polymer. For example, the first polymer, includingcarbonyl groups, is formed into the filter. The filter is then contactedwith the peroxymonosulfate to form a pendant dioxirane moiety on thepolymer. Alternatively, the polymer with a pendant dioxirane moiety isformed into a filter. In various embodiments, the article is a fluidfilter. For example, the fluid filter may be a gas filter or a liquidfilter. Gas filters include, but are not limited to, air filters. Thefilters may be constructed in the same way home air filters and HEPAfilters are constructed.

For example, a non-woven, fibrous substrate, such a filter, may bemanufactured with intermingled fibers to create an air-pervioussubstrate. Mats of randomly overlaid fibers may be produced bycommercially available non-woven manufacturing apparatus according tomethods described by the manufacturer thereof. For example, a suitableapparatus may be the RANDO-WEBBER® (Curlator Corporation, Rochester,N.Y.).

Once formed the fibrous substrate having a polymer fiber includingpendant carbonyl groups may be contacted with a mixture of water andperoxymonosulfate, as described above. A non-woven, air pervious fibroussubstrate may be formed in a conventional manner using a non-wovenmanufacturing apparatus. The substrate may be contacted to aperoxymonosulfate solution, e.g., by spraying, dipping, or the like toresult in dioxirane groups formed at the polymer from the pendantcarbonyl groups. The spent peroxymonosulfate solution may be collectedfor reclamation and recycling.

Fibrous substrates manufactured by such machines may include binders,adhesives, stiffeners and flame retardants, which may be applied aftertreatment with the peroxymonosulfate solution. The filtrationcharacteristics of the fibrous substrate may be determined by the fibersize, thickness of the fibrous substrate and type of binders used infabrication.

In a further aspect, a method of gas purification is provided includingpassing a gas through a filter, where the filter includes a polymerincluding a pendant dioxirane moiety and the gas includes a biologicalcontaminant or chemical contaminant. In another aspect, a method ofliquid purification is provided including passing a liquid through afilter, where the filter includes a polymer including a pendantdioxirane moiety and the liquid includes a biological contaminant orchemical contaminant.

In some embodiments, the method of gas purification further includespassing a gas through the filter, where the gas contains a biological orchemical contaminant. As the gas passes through the filter, thedioxirane moiety oxidizes the contaminant, resulting in reduction of thedioxirane moiety to a carbonyl, or ketone group. The filter may act totrap the oxidized contaminant, or allow the oxidized and deactivatedcontaminant to pass through, with the filter merely providing increasedsurface area for reaction of the polymer with the contaminant. Themethod may further include, after reaction with the contaminant,regenerating the dioxirane by reacting the ketone groups with aneffective amount of a peroxymonosulfate.

In another aspect, a method is provided including providing a filterincluding a polymer, the polymer including ketone moieties, andconverting the ketone moieties to dioxirane moieties by reacting thepolymer with peroxymonosulfate.

The present technology, thus generally described, will be understoodmore readily by reference to the following Examples, which are providedby way of illustration and are not intended to be limiting of thepresent technology.

EXAMPLES

General Procedure A: A mixture of water (1 L), sodium bicarbonate (2 M),and 2KHSO₅.KHSO₄.K₂SO₄ (2 M with respect to KHSO₅) is continuouslyflowed through the polymer (100 g) via mechanical stirrer for 1 h. Thesolution is removed by filtration with a Buchner funnel, then washedwith two 50 mL portions water, followed by aspiration to remove most ofthe water. The resulting polymer is then further dried by freeze-drying.

Example 1

Preparation of a representative polyalkylene terephthalate including apendant dioxirane moiety. The polyalkylene terephthalate can either beprepared according to known methods from 1,4-butanediol andterephthaloyl chloride or obtained commercially, such as from BASF (soldas ULTRADUR). At least one of the carbonyl groups of the polyalkyleneterephthalate is oxidized according General Procedure A. Such a processis illustrated in Scheme 1 where both carbonyl groups are converted todioxirantes, however it is to be understood that only one of the groupsmay be converted, and not every monomer unit in the polymer isnecessarily converted.

Example 2

Preparation of a representative poly(methyl)acrylate including a pendantdioxirane moiety, according to Scheme 2. Poly(methyl)acrylate can beprepared by known methods from methyl acrylate or obtained commercially.The poly(methyl)acrylate is oxidized according to General Procedure A.It should be noted that not every monomeric unit of the polymer mayinclude a dioxirane moiety.

Example 3

Preparation of a polylactate including a pendant dioxirane moiety,according to Scheme 3. Polylactic acid, an illustrative polylactate, anbe prepared via known methods or obtained commercially. Polylactic acidis oxidized according to General Procedure A.

Example 4

Preparation of a polycarbonate including a pendant dioxirane moiety.Poly(bisphenol A carbonate), an illustrative polycarbonate, can beprepared via known methods or obtained commercially. Poly(bisphenol Acarbonate) is oxidized according to General Procedure A. Such a processis illustrated in Scheme 4 where both carbonyl groups are converted todioxirantes, however it is to be understood that only one of the groupsmay be converted, and not every monomer unit in the polymer isnecessarily converted.

Example 5

Preparation of a polysaccharide including a pendant dioxirane moiety.Chitin, an illustrative polysaccharide, is available via known methodsor obtained commercially. Chitin is oxidized according to GeneralProcedure A. Such a process is illustrated in Scheme 5 where bothcarbonyl groups are converted to dioxirantes, however it is to beunderstood that only one of the groups may be converted, and not everymonomer unit in the polymer is necessarily converted.

Example 6

Preparation of a polyacetate including a pendant dioxirane moiety,according to Scheme 6. Polyvinylacetate is available via known methodsor obtained commercially. Polyvinylacetate is oxidized according toGeneral Procedure A.

Example 7

Preparation of a polystyrene maleic anhydride including a pendantdioxirane moiety. Polystyrene maleic anhydride is readily available viaknown methods or obtained commercially. Polystyrene maleic anhydride isoxidized according to General Procedure A. Such a process is illustratedin Scheme 7 where both carbonyl groups are converted to dioxirantes,however it is to be understood that only one of the groups may beconverted, and not every monomer unit in the polymer is necessarilyconverted.

Example 8

Preparation of a polyurethane including a pendant dioxirane moiety.Poly(4,4′-diphenylmethane diisocyanate 1,2-ethanediol), an illustrativepolyurethane, and related fibers are prepared by known methods, such asmethods described in Heiss, H. L. et al. Ind. Eng. Chem. 46, 1498-1503(1954) and U.S. Pat. Nos. 5,000,899 and 6,533,975 and referencestherein. The poly(4,4′-diphenylmethane diisocyanate 1,2-ethanediol) isoxidized according to General Procedure A. Such a process is illustratedin Scheme 8 where both carbonyl groups are converted to dioxirantes,however it is to be understood that only one of the groups may beconverted, and not every monomer unit in the polymer is necessarilyconverted.

Example 9

Preparation of a modified polyamide including a pendant dioxirane moietyand a quaternary amine, according to Scheme 9. Poly(caprolactam) (“Nylon6”) is prepared via known methods or obtained commercially.Poly(caprolactam) is exhaustively methylated by adapting publishedmethods [Org. Synth. Coll. Vol. 5, 315 (1973) and references therein],to form an illustrative polyamide.

Example 10

Preparation of a modified polyacrylamide including a pendant dioxiranemoiety, according to Scheme 10. Polyacrylamide with a molecular weightrange of 5,000,000-6,000,000 is available by known methods andcommercial sources such as Sigma-Aldrich and Acros Organics.Polyacrylamide is exhaustively methylated by adapting published methods[Org. Synth. Coll. Vol. 5, 315 (1973) and references therein], to forman illustrative polyacrylamide. 100 g of the modified polyacrylamide isthen added to a mixture of water (1 L), sodium bicarbonate (2 M), and2KHSO₅.KHSO₄.K₂SO₄ (2 M w/r KHSO₅)) and stirred via magnetic stirbar formechanical 1 h. The polymer is then purified by dialysis againstdistilled water using a dialysis membrane (molecular weightcutoff=1000). Freeze drying provides the modified polyacrylamideincluding a pendant dioxirane moiety.

Example 11

Preparation of a modified polyacrylamide including a pendant dioxiranemoiety, according to Scheme 11. Polydimethylacrylamide, an illustrativepolyacrylamide, is prepared according to Isaure, F. et al. React. Funct.Polym. 66, 65-79 (2006). Polydimethylacrylamide is then exhaustivelymethylated by adapting published methods [Org. Synth. Coll. Vol. 5, 315(1973) and references therein]. 100 g of the methylatedpolydimethylacrylamide is then added to a mixture of water (1 L), sodiumbicarbonate (2 M), and 2KHSO₅.KHSO₄.K₂SO₄ (2 M w/r KHSO₅)) and stirredvia magnetic stirbar for mechanical 1 h. The polymer is then purified bydialysis against distilled water using a dialysis membrane (molecularweight cutoff=1000). Freeze drying provides the modified polyacrylamideincluding a pendant dioxirane moiety.

Example 12

Preparation of a poly(methyl)methacrylate including a pendant dioxiranemoiety, according to Scheme 12. Poly(methyl)methacrylate, anillustrative methacrylate polymer, is available by known methods andcommercial sources such as Sigma-Aldrich. Poly(methyl)methacrylate isoxidized according to General Procedure A.

Example 13

Preparation of an aramid including a pendant dioxirane moiety.Poly-paraphenylene terephthalamide, an illustrative aramid, is availableby known methods, such as the combination of para-phenylene diamine andterephthaloyl dichloride, and commercial sources such as DuPont (sold asKEVLAR). Poly-paraphenylene terephthalamide is oxidized according toGeneral Procedure A. Such a process is illustrated in Scheme 13 whereboth carbonyl groups are converted to dioxirantes, however it is to beunderstood that only one of the groups may be converted, and not everymonomer unit in the polymer is necessarily converted.

Example 14

Preparation of a polyurea including a pendant dioxirane moiety. Spandexis available by known methods and from commercial sources such asInvista. Spandex, an illustrative polyurea, is oxidized according toGeneral Procedure A. Such a process is illustrated in Scheme 14 whereboth carbonyl groups are converted to dioxirantes, however it is to beunderstood that only one of the groups may be converted, and not everymonomer unit in the polymer is necessarily converted.

Example 15

Preparation of a modified polyurea including a pendant dioxirane moiety.Spandex is exhaustively methylated by adapting published methods [Org.Synth. Coll. Vol. 5, 315 (1973) and references therein], to form anillustrative modified polyurea. 100 g of the methylated spandex is thenadded to a mixture of water (1 L), sodium bicarbonate (2 M), and2KHSO₅.KHSO₄.K₂SO₄ (2 M w/r KHSO₅)) and stirred via magnetic stirbar formechanical 1 h. The polymer is then purified by dialysis againstdistilled water using a dialysis membrane (molecular weightcutoff=1000). Freeze drying provides the modified spandex including apendant dioxirane moiety. Such a process is illustrated in Scheme 15where both carbonyl groups are converted to dioxirantes, however it isto be understood that only one of the groups may be converted, and notevery monomer unit in the polymer is necessarily converted.

Example 16

Preparation of a polymer including a perfluoro stabilized pendantdioxirane moiety, according to Scheme 16.1,1,1-trifluoro-3,3,4-trimethylpent-4-en-2-one, an illustrative polymerwith a pendant perfluoro group, is prepared according to publishedmethods [Nenajdenko, V. G. Tetrahedron 50, 11023-11038 (1994)].1,1,1-trifluoro-3,3,4-trimethylpent-4-en-2-one is polymerized byadapting published methods [Zhang, J. et al. Macromolecules 35, 8869-77(2002); Monieau, C. et al. Macromolecules 32, 8277-82 (1999); Gilmer, T.C. et al. J. Polym. Sci. Pol. Chem. 34, 1025-37 (1996) and referencestherein]. Poly(1,1,1-trifluoro-3,3,4-trimethylpent-4-en-2-one) isoxidized according to General Procedure A.

Example 17

Preparation of a branched backbone polymer including a perfluorostabilized pendant dioxirane moiety, according to Scheme 17.4-ethoxy-1,1,1-trifluorobut-3-en-2-one, an illustrative branchedpolymer, is available by known methods and commercially fromSigma-Aldrich. 4-ethoxy-1,1,1-trifluorobut-3-en-2-one is polymerized byadapting published methods [Zhang, J. et al. Macromolecules 35, 8869-77(2002); Monieau, C. et al. Macromolecules 32, 8277-82 (1999); Gilmer, T.C. et al. J. Polym. Sci. Pol. Chem. 34, 1025-37 (1996) and referencestherein]. Poly(4-ethoxy-1,1,1-trifluorobut-3-en-2-one) is oxidizedaccording to General Procedure A.

Example 18

Preparation of a poly(methyl-2-keto-3-butenoate) including a pendantdioxirane moiety, according to Scheme 18. Methyl-2-keto-3-butenoate isprepared from commercially available 2-keto-3-butenoic acid by adaptingpublished methods [Org. Synth. Coll. Vol. 3, 610 (1995) and referencestherein]. Methyl-2-keto-3-butenoate is polymerized by adapting publishedmethods [Zhang, J. et al. Macromolecules 35, 8869-77 (2002); Monieau, C.et al. Macromolecules 32, 8277-82 (1999); Gilmer, T. C. et al. J. Polym.Sci. Pol. Chem. 34, 1025-37 (1996) and references therein].Poly(methyl-2-keto-3-butenoate) is oxidized according to GeneralProcedure A.

Example 19

Preparation of a poly(methyl-2-keto-4-pentenoate) including a pendantdioxirane moiety, according to Scheme 19. Methyl-2-keto-4-pentenoate isprepared from commercially available 2-keto-4-pentenoic acid by adaptingpublished methods [Org. Synth. Coll. Vol. 3, 610 (1995) and referencestherein]. Methyl-2-keto-4-pentenoate is polymerized by adaptingpublished methods [Zhang, J. et al. Macromolecules 35, 8869-77 (2002);Monieau, C. et al. Macromolecules 32, 8277-82 (1999); Gilmer, T. C. etal. J. Polym. Sci. Pol. Chem. 34, 1025-37 (1996) and referencestherein]. Poly(methyl-2-keto-4-pentenoate) is oxidized according toGeneral Procedure A.

Example 20

Filtering a liquid with the polymer. A plug of disinfected glass wool isplaced in the bottom of a glass column. The glass column is then filledwith 100 g of the dioxirane bearing poly(methyl-2-keto-3-pentenoate)from Example 18. 300 mL of water bearing biological contaminants is thengently placed in the column. The water is then allowed to move throughthe polymer and into a receiving flask. Use of the polymer as a filteroxidizes the biological contaminants in the water. The filter may alsotrap the oxidized contaminants, or the oxidized biological contaminantsremain with the water but their activity is substantially reduced oreliminated as a result of the oxidation.

Example 21

Regenerating a liquid filter. A solution of water (1 L), sodiumbicarbonate (2 M), and 2KHSO₅.KHSO₄.K₂SO₄ (2 M with respect to KHSO₅) ismade (the “peroxymonosulfate solution”). The liquid filter of Example20, after filtration, is loaded with a 300 mL of the peroxymonosulfatesolution. The solution is then allowed to move through the polymer andinto a receiving flask to regenerate the dioxirane moieties and helpremove degraded contaminants. This may be repeated 2 more times withfresh peroxymonosulfate solution. The liquid filter may then be flushedwith two 100 mL portions of distilled water to remove any remainingsalts from the regeneration.

Example 22

Making an air filter. Polylactic acid including a pendant dioxiranemoiety from Example 3 is pressed into porous sheets. The sheets are thenpleated and connected to a steel screen by glue around the edges of thesteel screen.

Example 23

Making an air filter using two polymers. Polylactic acid including apendant dioxirane moiety from Example 3 andpoly(methyl-2-keto-4-pentenoate) including a pendant dioxirane moietyfrom Example 19 are pressed together into porous sheets. The sheets arethen pleated and connected to a steel screen by glue around the edges ofthe steel screen.

Example 24

Use of an air filter from Example 23. The air filter of Example 23 isplaced in a home HVAC system in the filter holder. The HVAC system isturned on and allowed to work according to its design. Use of the filterin the HVAC system removes biological contaminants and chemicalcontaminants from the air in the home.

Example 25

Recycling of an air filter from Example 24. After the dioxirane moietieson the polymer filter have been substantially reduced, or after apre-determined time period, the dioxirane moieties on the polymer filtermay be regenerated. The filter may be sprayed or dipped in an aqueousperoxymonosulfate solution. The solution may include potassiumperoxymonosulfate (OXONE®, DuPont, Wilmington Del.) at a concentrationof 25 milliMolar; sodium bicarbonate (Sigma-Aldrich, St. Louis, Mo.) toadjust the pH to about 7; and cetyl trimethylammonium bromide(Sigma-Aldrich, St. Louis, Mo.) at a concentration of about 1milliMolar. After spraying or dipping the filter, the carbonyl groups onthe polymer are thus converted to the pendant dioxirane moieties to“recharge” or “recycle” the filter. After spraying or dipping thefilter, the filter may be rinsed with distilled water.

Equivalents

While certain embodiments have been illustrated and described, it shouldbe understood that changes and modifications can be made therein inaccordance with ordinary skill in the art without departing from thetechnology in its broader aspects as defined in the following claims.

The embodiments, illustratively described herein may suitably bepracticed in the absence of any element or elements, limitation orlimitations, not specifically disclosed herein. Thus, for example, theterms ‘comprising,’ ‘including,’ ‘containing,’ etc. shall be readexpansively and without limitation. Additionally, the terms andexpressions employed herein have been used as terms of description andnot of limitation, and there is no intention in the use of such termsand expressions of excluding any equivalents of the features shown anddescribed or portions thereof, but it is recognized that variousmodifications are possible within the scope of the claimed technology.Additionally, the phrase ‘consisting essentially of’ will be understoodto include those elements specifically recited and those additionalelements that do not materially affect the basic and novelcharacteristics of the claimed technology. The phrase ‘consisting of’excludes any element not specified.

The present disclosure is not to be limited in terms of the particularembodiments described in this application, which are intended asillustrations of various aspects. Many modifications and variations canbe made without departing from its spirit and scope, as will be apparentto those skilled in the art. Functionally equivalent compositions,apparatuses, and methods within the scope of the disclosure, in additionto those enumerated herein, will be apparent to those skilled in the artfrom the foregoing descriptions. Such modifications and variations areintended to fall within the scope of the appended claims. The presentdisclosure is to be limited only by the terms of the appended claims,along with the full scope of equivalents to which such claims areentitled. It is to be understood that this disclosure is not limited toparticular methods, reagents, compounds compositions or biologicalsystems, which can, of course, vary. It is also to be understood thatthe terminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting.

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, particularly in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as ‘up to,’ ‘at least,’ ‘greater than,’ ‘less than,’ and the like,include the number recited and refer to ranges which can be subsequentlybroken down into subranges as discussed above. Similarly, the phrase “atleast about” some value such as, e.g., wt % includes at least the valueand about the value. For example “at least about 1 wt %” means “at least1 wt % or about 1 wt %.” Finally, as will be understood by one skilledin the art, a range includes each individual member.

Other embodiments are set forth in the following claims.

What is claimed is:
 1. A polymer comprising at least one pendantdioxirane moiety represented by Formula I or II:

wherein: the carbon atom of Formula II is in a polymer chain of thepolymer; R¹ is alkylene, perhaloalkylene, carbonyl, carboxyl,alkylcarboxyl, carboxyalkyl, or alkylcarboxyalkyl; R² is an electronwithdrawing group; and R³ is H, alkyl, perhaloalkyl, cycloalkyl, aryl,heteroaryl, heterocyclyl, amino, carbonyl, carboxyl, alkylcarboxy,carboxyalkyl or alkylcarboxyalkyl.
 2. The polymer of claim 1, whereinthe pendant dioxirane moiety is represented by Formula I, and wherein:R² is —N⁺R⁴R⁵R⁶, halogen, NO₂, C(O)H, CO₂R⁷, alkoxy, or perhaloalkyl; R⁴is H, alkyl, or cycloalkyl; R⁵ is H, alkyl, or cycloalkyl; R⁶ is H,alkyl, or cycloalkyl; and R⁷ is H, alkyl, or cycloalkyl.
 3. The polymerof claim 1, wherein R² is perfluoroalkyl.
 4. The polymer of claim 1,wherein the polymer is a polyolefin, a polyalkylene terephthalate, apolyacrylate, a polylactates, a polycarbonate, a polyester, apolysaccharide, a polyacetate, a polystyrene maleic anhydride, apolyurethane, a polyamide, a polyacrylamide, a polymethacrylates, apoly(methyl)methacrylate, an aramid, a co-polymer of any two or moresuch polymers, or a blend of any two or more such polymers.
 5. Thepolymer of claim 1 represented by Formula II.
 6. The polymer of claim 1which is:


7. A polymer comprising at least one pendant dioxirane moietyrepresented by Formula IV:

wherein: the carbon atom of Formula IV is in a polymer chain of thepolymer; R⁸ is —N⁺R⁴R⁵ or alkyl; R⁹ is —N⁺R⁴R⁵ or alkyl; each R⁴ isindependently H, alkyl, or cycloalkyl; and each R⁵ is independently H,alkyl, or cycloalkyl.
 8. The polymer of claim 7, wherein the polymer isa polyolefin, a polyalkylene terephthalate, a polyacrylate, apolylactates, a polycarbonate, a polyester, a polysaccharide, apolyacetate, a polystyrene maleic anhydride, a polyurethane, apolyamide, a polyacrylamide, a polymethacrylates, apoly(methyl)methacrylate, an aramid, a co-polymer of any two or moresuch polymers, or a blend of any two or more such polymers.
 9. A polymercomprising at least one pendant dioxirane moiety represented by FormulaI:

wherein: R¹ is alkylene, perhaloalkylene, carbonyl, carboxyl,alkylcarboxyl, carboxyalkyl, or alkylcarboxyalkyl; R² is an electronwithdrawing group; and R³ is H, alkyl, perhaloalkyl, cycloalkyl, aryl,heteroaryl, heterocyclyl, amino, carbonyl, carboxyl, alkylcarboxy,carboxyalkyl or alkylcarboxyalkyl.
 10. The polymer of claim 9, wherein:R² is —N⁺R⁴R⁵R⁶, halogen, NO₂, C(O)H, CO₂R⁷, alkoxy or perhaloalkyl; R⁴is H, alkyl, or cycloalkyl; R⁵ is H, alkyl, or cycloalkyl; R⁶ is H,alkyl, or cycloalkyl; and R⁷ is H, alkyl, or cycloalkyl.
 11. The polymerof claim 9, wherein R² is perfluoroalkyl.
 12. The polymer of claim 9,wherein the polymer is a polyolefin, a polyalkylene terephthalate, apolyacrylate, a polylactates, a polycarbonate, a polyester, apolysaccharide, a polyacetate, a polystyrene maleic anhydride, apolyurethane, a polyamide, a polyacrylamide, a polymethacrylates, apoly(methyl)methacrylate, an aramid, a co-polymer of any two or moresuch polymers, or a blend of any two or more such polymers.
 13. Thepolymer of claim 9 which is: